Modern Heterogeneous Oxidation Catalysis: Design, Reactions and Characterization

Modern Heterogeneous Oxidation Catalysis: Design, Reactions and Characterization......Page 2
Contents......Page 8
Preface......Page 14
List of Contributors......Page 16
1.1 Introduction......Page 20
1.2 The Research Field......Page 23
1.3 Substrate Activation......Page 26
1.4 Active Oxygen Species......Page 34
1.5 Catalyst Material Science......Page 41
1.6 Conclusion......Page 53
References......Page 54
2.1 Introduction......Page 62
2.2.1 Asymmetric Heterogeneous Catalysis Using Supported Metal Complexes......Page 63
2.2.2 Chiral V-Dimer Structure on a SiO2 Surface......Page 64
2.2.3 Asymmetric Catalysis for Oxidative Coupling of 2-Naphthol to BINOL......Page 68
2.3.1 Preferential Oxidation (PROX) of CO in Excess H2 on Novel Metal Catalysts......Page 70
2.3.2 Characterization and Performance of a Novel Cu Cluster/CeO2 Catalyst......Page 71
2.4.1 Phenol Production from Benzene with N2O, H2 + O2, and O2......Page 76
2.4.1.1 Benzene to Phenol with N2O......Page 77
2.4.1.2 Benzene to Phenol with H2 + O2......Page 79
2.4.1.3 Benzene to Phenol with O2......Page 81
2.4.2 Novel Re/HZSM-5 Catalyst for Direct Benzene-to-Phenol Synthesis with O2......Page 83
2.4.3 Active Re Clusters Entrapped in ZSM-5 Pores......Page 85
2.4.4 Structural Dynamics of the Active Re10 Cluster......Page 87
References......Page 90
3.1 Introduction......Page 96
3.2.1.1 Junction Perimeter Between Au Particles and the Support......Page 98
3.2.1.2 Selection of Suitable Supports......Page 100
3.2.1.3 Sensitivity to the Size of the Gold Particles......Page 101
3.2.2 Low-Temperature CO Oxidation in H2......Page 103
3.2.3.1 Mechanisms Involving Junction Perimeter Between Gold and the Metal-Oxide Supports......Page 106
3.2.3.2 Mechanisms Involving Specific Size or Thickness of Gold Clusters or Thin Layers......Page 109
3.3 Complete Oxidation of Volatile Organic Compounds......Page 111
3.4.1 Gas-Phase Selective Oxidation of Aliphatic Alkanes......Page 116
3.4.2 Gas-Phase Selective Oxidation of Alcohols......Page 117
3.4.3.1 Introduction......Page 119
3.4.3.2 Gas-Phase Propylene Epoxidation with Hydrogen–Oxygen Mixtures on Au/TiO2......Page 120
3.4.3.3 Gas-Phase Propylene Epoxidation with Hydrogen–Oxygen Mixtures on Au/Ti-SiO2......Page 122
3.5 Liquid-Phase Selective Oxidation of Organic Compounds......Page 125
3.5.1 Oxidation of Mono-Alcohols......Page 126
3.5.2 Oxidation of Diols......Page 131
3.5.3 Oxidation of Glycerol......Page 132
3.5.4 Aerobic Oxidation of Glucose......Page 134
3.6 Conclusions......Page 135
References......Page 137
4.1 Introduction – Two Ways to Introduce Hetero-Metals into Zeolites......Page 144
4.2.1 TS-1......Page 145
4.2.2 Ti-Beta......Page 155
4.2.3 Ti-MWW......Page 156
4.2.5 Solvent Effects and Reaction Intermediate......Page 164
4.3 Other Metal-Containing Zeolites......Page 169
References......Page 170
5.2 Oxidation of Alcohols......Page 176
5.2.1 Ru Catalyst......Page 177
5.2.2 Pd Catalyst......Page 182
5.2.3 Au Catalyst......Page 183
5.3 Epoxidation of Olefins......Page 185
5.3.1.2 Tungsten-Based Catalysts......Page 186
5.3.1.3 Base Catalyst......Page 188
5.3.2 Epoxidation with Molecular Oxygen......Page 191
5.4 Cis-Dihydroxylation......Page 192
5.5 Baeyer–Villiger Oxidation......Page 194
5.6 C–H Activation Using Molecular Oxygen......Page 196
References......Page 197
6.1 Introduction......Page 204
6.2 Molecular Design of Polyoxometalates for H2O2- and O2-Based Oxidations......Page 205
6.2.1 Isopoly- and Heteropolyoxometalates......Page 207
6.2.2 Peroxometalates......Page 208
6.2.3 Lacunary Polyoxometalates......Page 209
6.2.4 Transition-Metal-Substituted Polyoxometalates......Page 211
6.3 Heterogenization of Polyoxometalates......Page 212
6.3.1.1 Metal and Alkylammonium Cations......Page 219
6.3.1.2 Polycations......Page 220
6.3.1.3 Cationic Organometallic Complexes......Page 222
6.3.2.1 Wet Impregnation......Page 224
6.3.2.2 Solvent-Anchoring and Covalent Linkage......Page 226
6.3.2.3 Anion Exchange......Page 227
6.4 Conclusion......Page 229
References......Page 230
7.1 Introduction......Page 236
7.2 Molecular Structure and Physical Properties of Nitrous Oxide......Page 237
7.3.1 Oxidation of Lower Alkanes Over Oxide Catalysts......Page 239
7.3.2.1 Oxidation by Dioxygen......Page 241
7.3.2.2 Oxidation of Benzene to Phenol by N2O......Page 242
7.3.2.3 Nature of Zeolite Activity, α-Sites......Page 243
7.3.2.4 N2O specificity, α-Oxygen and its Stoichiometric Reactions......Page 246
7.3.2.5 Hydroxylation of Alkanes and Benzene Derivatives......Page 248
7.4 Catalytic Oxidation by N2O in the Liquid Phase......Page 249
7.5.1 Liquid-Phase Oxidation of Alkenes......Page 250
7.5.1.1 Linear Alkenes......Page 251
7.5.1.2 Cyclic Alkenes......Page 253
7.5.1.3 Cyclodienes......Page 256
7.5.1.5 Heterocyclic Alkenes......Page 257
7.5.2.1 Carboxidation of Polyethylene......Page 259
7.5.2.2 Carboxidation of Polybutadiene Rubber......Page 260
7.6.1 Recovery of N2O From Off-Gases......Page 263
7.6.2 Deliberate Preparation of N2O......Page 264
7.7 Conclusion......Page 265
References......Page 266
8.1.1 Industrial Production......Page 272
8.1.2 Outlook for H2O2 Production......Page 273
8.1.3 Uses of Hydrogen Peroxide......Page 274
8.2.1 Status of Development and Perspectives of Industrial Production......Page 276
8.2.2 Recent Patents on the Direct Synthesis of H2O2......Page 281
8.3 Fundamental Studies......Page 289
8.3.1 Intrinsically Safe Operations and Microreactors......Page 290
8.3.2 Nature of the Catalyst and Reaction Network......Page 294
8.3.3 Role of the Solvent and of Promoters......Page 300
8.4 Conclusion......Page 301
References......Page 302
9.1 Introduction: Old and New Challenges for Oxidation Catalysis in Industry......Page 308
9.2.1 Oxidation of Ethane to Acetic Acid......Page 309
9.2.2 Ammoxidation of Propane to Acrylonitrile......Page 313
9.3 New Oxidation Technologies: Oxidative Desulfurization (ODS) of Gas Oil......Page 320
9.4 Process Intensification in Catalytic Oxidation......Page 323
9.5 An Alternative Approach: Anaerobic Oxidation with Metal Oxides in a Cycle Process (from an Oxidation Catalyst to a Reusable Stoichiometric Oxidant)......Page 325
9.5.1 Anaerobic Oxidation of Propene to Acrolein in a CFBR Reactor......Page 328
9.5.2 Anaerobic Synthesis of 2-Methyl-1,4-Naphthoquinone (Menadione)......Page 329
9.5.3 Anaerobic Oxidative Dehydrogenation of Propane to Propene......Page 330
9.5.4 Production of Hydrogen from Methane with Oxide Materials and Inherent Segregation of Carbon Dioxide......Page 332
9.6 Current and Developing Processes for the Transformation of Bioplatform Molecules into Chemicals by Catalytic Oxidation......Page 335
9.6.1 Glycerol: A Versatile Building Block......Page 339
9.7 Conclusion......Page 340
References......Page 342
Index......Page 352